Indazole azo dyestuff



Patented Mar. 13, 1951 UNI-TED STATES PATENT OFFICE INDAZOLE AZO DY ES'I UFF Pierre Petitcolas, Rouem-Robert Frederic Michel 1 Sureau, ,Mont- St.-Aignan,

and Andr Paul Richard, Oissel, France, assignors to Societe Anonyme dc Matieres Colorantes et Produits Chimiques Francolor, Paris, France, a French company 1 Claim. ((21. 260-157) A long While ago acetoacetyl derivatives of nen-t and one in the diazo component; i. e. A, 3

amino azo compounds of. the benzene series were proposed for use as coupling components for ice colours. However these derivatives have never found industrial application, probably because of lack of fastness and brightness of the shades obtained.

It has now been found that disazo and trisazo dyestuffs obtained by coupling, in bulk or on the fibre respectively, a diazo ortetrazo component, not containing other solubilising groups than the dlazo group, with a coupling component consisting of an acetoacetyl derivative of respectively a monoaminoazo ordiaminoazo compound, are of industrial importance if they contain in their molecule one or more 'indazole, benzimidazol, or benztriazole nuclei. A

Such dyestuffs have the general formula:

(A-N=N irnngco-cnz-co-cna) n If-.-a nucleus selected from the group which on'si stsof indazole, benzimidazole and benztrip.a'zole nuclei be referred to as a Z nucleus, the

- Z nuclei maybe distributed as follows in the .molecule of the dyest'ufij ....(1) No Z nucleus inthe coupling compognent and one in the diazo component; i. e., X

a fZ nucleus and A and B are benzene nuclei.

(2) One Z nucleus 'in the coupling compo.- nent and none in the diazo component; i. e., X abenzene nucleus 'andeither A is a Z nucleus and B is a benzene nucleus or B is a Z nucleus and A is a benzene nucleus.

. 3) 'IIwo Z nuclei in the coupling compo- ?nentand none in 'the dia'zo component; i. e. A cl- B are Zf nuclei and X is a benzene nucleus.

$4) One Z nucleus in the coupling compo- A and X are Z-"nuclei and B' is a benzene nucleus or B andX are Z nuclei and A is a benzene nucleus.

andX are all Z nuclei. 1 The acetcacetylamine chain or chains can be situated ortho or para to the azo linkage be tween A and B of the coupling component.

In the second and fourth cases defined above,

in the case of a" mono acetoacetylamino compound, the acetoacetylamino group can be on the indazole, benzimidazole or benztriazole nucleus, or else on the nucleus attached to this by the azo linkage of the coupling component; i. e. it may be on the, A or B nucleus.

Whatever may be, moreover, the relative positionof the vindazole, benzimidazole or benztri I lie lakes. Thisproperty'allows of obtaining a hem and one in thediazo component; i. e. either obtaining greens in certain cases,

whole range of brown shades from yellowish browns to blacks, passing through reddish browns and violet or corinth browns, and even of In particular it has been found that when the molecule of the coupling component contains one or two indazole, benzimidazole or benztri- .azole' nuclei (i. e. when either A or B or both of .them is or are Z nuclei) and presents the following characteristics: I

(1) a heterocyclic nuclear nitrogen ortho to the azo linkage;

(2) an alkoxy group ortho to the same link age, coppering brings out a much more consid- "erable deepening of colour than if these conditions. are not realised, leading thus to ,negro head browns, corinth browns and even blacks. It is also in this category that thegreen com,- binations obtained after coppering occur.,

.7 Finally; in all cases, but especially in those which have, just been mentioned coppering brings about a very considerable improvementln fastnessto different tests and in particular to light.

.The .amino indazoles, amino benzimidazoles, -and amino .benztriazoles used in the preparation of the dyestuffs according. to theinvention-are obtained by processes already described inchemical literature. I

From these amlnes,.used as .diazo components or coupling components there are prepared/according. to general :known methods, aminoazo compounds whichmay be then condensed with acetoacetic, esters to transform them into acetoacetylamino azo compounds.

Two .Z. nuclei in he coup in omm- 5 Acetoacetyl groups can also introduced into the azo derivatives of benzimidazoles, indazoles, or benztriazoles by reduction of nitro groups and acetoacetylation, or by saponification of aceto-. amino groupsv and acetoacetylation.

The fixing on the fibre of dyestuffs in accord ance with the inventions can be brought about by dyeing, foularding or printing, directly or on passing through the intermediate stages of. pitrosamine or Schifis base and in general according to all the known techniques which may be used for ice colours.

An azo dyestufi of the general formula I ii&N=NB Nnooo=owmom N=NX V in which A, B and X are nuclei at least "one of which is an indazole, benzimidazole or benztri azole nucleus, X being free from solubilising groups, is prepared, according;v to the invention, by diazotising a compound of the formula XNH: and coupling it with a. compound of the general formula A I\T=NB HCOCHiQOCH;

:The following examples illustrate, without limiting, the invention.

' I Emmpt e 1' By diazotisati'on of 7-amino-indazole and coupling with amino-2:5-dim'ethoxyaniline there is obtained an aminoazo derivative or the constitution.

, NH ENC? CH: 13111 H which is acetoacet'yl'ated according to the following method: In an apparatus provided with a first reflux condenser, inwhich circulates a current of steam, and withfia' second reflux condenser in which; circulates a current of e'oid 'water,--there is heated upto commencement of distillation 600 g. of chlorobenzene 25., g. of acetoacetic ester l g. of triethanolamine Then there is introduced, over three quartersof "an hour, with stirring, a filtered Solution, kept at a temperature near boiling of 30 g. of l-amino-2:5-dimethoxybenzene azo-l-dndazole in 600 g. of chlorobenz'ene.

heated for an hour more after the end of the introduction of the above mentioned solution'so as to drive off in all 920 parts of chlorobenz'ene.

'It allowed to' cool while stirring, the'acetoe acetyl derivative crystallisa in fine brick red crystals;

It is filtered, sucked dry, washed with benzene Denatured ethyl arsenal 20 cc. W. r 0, j

36 B. caustic soda Sec.

and this solution is allowed to flow into a solu-, tion containing Water 1000 cc;

Caustic soda 36 Be. 10'- Anhydrous sulphate of soda 40 g. Sulphoricinate of soda 5 cc.

Crystalline copper sulphate 2.5 g. Monoethanolamine- 5 g. Water 1000 g.

After rinsing it is boiled. for half an hour in a bath containing 1.5 g. litre of sodium carbonate and and 1.5 g. litre of soda soap having oi fatty material".

There is obtained a. brownish black shade of excellent properties as regards. fastness in particular to light.

Example 2" 4 parts of the product corresponding the formula are pasted in 10 g. warm. methyl alcohol. There is added 1 cc. of caustic soda. of 36 B. The limpid solution. thus obtained poured into the following solution:

Cold water up to. 1000 g. Anhydrous sodium sulphate 40 g. Sulphoricinate of soda 5 g.

Caustic soda 36 B6. 10cc".

'50 g. or cotton are immersed iii this bath f half an hour. The cotton is then pressed. out' in the cold and developed, according to the usual technique for ice colours, in a bath b11000 g. of water containingl5 g. of the diazo salt of an aminoanthraquinone stabilised at 20% base.

After developing and rinsing the fibre is treated for half an hour at C. in the following bath Copper sulphate (crystalline) 2.5-8 Monoethanolamine 5 g. Water 1000 g.

Q It is finally rinsed and boiled for half. an hour .in a bath containing 2 grams per litre sodium carbonate'andv 2 grams per litre Marseilles soap. After rinsing and drying there is obtained a sepia brown of excellent fastness.

Ecdmple '3 There isdiss'ol'ved in 10 xor methyl alcohol and ill do.- of 36 "B. caustic soda, 4 g. of the product of the following formula:

on NH-N I 5 MOL 10 The alcoholic solution is poured into the following bath Cold water up to 1000 g. Anhydrous sodium sulphate 30 g. Sulphoricinate of soda 5 g. Caustic soda 36 B. 10 cc.

50 g. of cotton are worked in this for half an hour, pressed out and developed in a bath of 152;. per litre of the stabilised diazo compounds of o-nitraniline of 20%, suitably neutralised. Itis finished as in Example 1 and there is obtained a chocolate brown of good fastness.

- Ezcample 4 In operating with a product of the formula 60151: NHCOCHaCOOHa Coupling component Diazo component Shade on, c1

=N CH Dull ne I0 head 7 \N bi'own. cmoocmc ONH Nncoontcoom NH/ H. NH,

omoocmcoNn Nncocmcocm NH/ 7 l 7 NH N N0 0CH| 7 Yellow brown. OCH: OH H NH, C -N= @mrooomcoom 01 NH Bl t z OCH: N= Nncocmoocn,

m I 7 No 00H. Reddish brown.

CH\ Negro head.

N NE/ 7 v 7 NH:

NH 1) 11 i th 1 l] 001' n OCH; 1(3 EH brown.

01 cmcocmc ONH N=N OCHl D0 0 0 Dull negro head.

iii-#59329 Chocolatebi-own.

CEaO N=N Nncocmoocm Do NH, Violet brown.

' N\ B lhblak o rowns c v. OOH 6 CH CH|COCH:CONH-C 1N=NCI OCH:

i C (H CH 5 CMOCWNHQMG I em 161E11 ocm NH oocm6ocfi,

. 0H1o 161 CH N=N I on. l m-cocmcobm /N\ mm NH 1;:

cm NHCOCHaCOCH: Ibis /N\ I N NE" (Rom CWCHMHQMQ Hz 011, no

Black brown.

Negro head.

Green bronze.

Ollve brown.

Bordeaux brow-n.

Dull chocolate brown.

Coupling component Diazo component Shade N NH; Chocolate brow-n. IIIH (3H NH-N ll 01- N 0, IYH- N=N CH (3 O CH2 +0 CH3 Do NH, Chocolate brown, yellower than the foregoing. CH3 0 N 05 Do NH NH; Dull negro head.

N D u 11 c h a m o i 8 NH; brown. N IIIH NH--N H d! N=N CH l IHC 0 CHzC O CH:

/ NE R dd h b e 15 rown. OH NH NH 2 Y Cl N=N NHC OCHQC OCH:

; N0 NH, Ne 0 head. CH NH NBC- N at it CH 0 CH: N=N

NHCOCHzCOCE 01 D CH Do.

N NH We declare that what we claim is:

A copperable azo dyestuff of the general in which X is a benzene nucleus free from solubilising groups, B is a benzene nucleus having an alkoxy group in the ortho position to the azo linkage shown between A and B and A is an no indazole nucleus having an imino nitrogen atom in the ortho position to the azo linkage shown between A and B.

PIERRE PETITCOLAS.

REFERENCES CITED file of this patent:

UNITED STATES PATENTS The following references are of record in the ROBERT FREDERIC MICHEL SUREAU. u

ANDRE PAUL RICHARD. 

